1. Field of the Invention
The invention lies in the technological field of PEM fuel cells and pertains, more specifically, to a method for discharging reaction water in PEM fuel cells and to a PEM fuel cell for implementing the method.
The operation of fuel cells gives risexe2x80x94in the course of the electrochemical reaction of hydrogen (H2) with oxygen (O2)xe2x80x94to water (H2O). In PEM fuel cells (PEM=polymer electrolyte membrane), in which a cation exchange membrane serves as the electrolyte, the protons (H+) formed at the anodexe2x80x94via oxidation of the hydrogenxe2x80x94diffuse through the membrane and at the cathode combine with the O2xe2x88x92 ions produced there to form water. The reaction water must be removed from the fuel cell so as not to affect the water budget and to keep it constant.
Various options of discharging the reaction water from PEM fuel cells are known:
Discharge from the cathode side (in liquid phase):
The reaction gases are humidified to completion (saturation concentration) at the operating temperature, e.g. about 60 to 80xc2x0 C. The reaction water is then produced as a liquid and is carried off in the transport gas, from the cathode gas space by means of a gas excess (see Proceedings of the 26th Intersoc. Energy Conversion Eng. Conf., Boston, Mass., Aug. 4 to 9, 1991, Vol. 3, pp. 630-35; the publication also discloses the design principles for a PEM fuel cell).
If the cell is operated with air, the transport gas can be the inert gas fraction nitrogen (N2). A drawback of that process is that the humidification of the reaction gases is relatively involved.
Discharge on the cathode side (partially or completely in vapor phase):
The reaction gases are not humidified or only partially humidified, so that the reaction water can be discharged, at least in part, as a vapor (see U.S. Pat. No. 5,260,143 and European patent EP 0 567 499 B1). That type of operational approach places certain requirements on the electrolyte membrane in terms of mechanical stability and conductivity. In systems employing elevated working pressures it is possible to convert the reaction water into the vapor phase via expansion stages and to remove it from the fuel cell. Such a procedure is very involved however.
Discharge on the anode side:
The operational approaches in which the reaction water is discharged on the anode side employ a pressure differentialxe2x80x94of the reactantsxe2x80x94between cathode and anode (see U.S. Pat. No. 5,366,818). There, elevated gas pressure on the cathode side, e.g. air at 4xc2x7105 Pa (4 bar) compared with hydrogen at 2xc2x7105 Pa (2 bar), is employed to force the reaction water to the anode side where it is removed from the fuel cell by means of excess hydrogen. Setting an elevated pressure (on the cathode side) has severe drawbacks, however, since compression requires energy.
Furthermore, U.S. Pat. No. 5,272,017 and published European patent application EP 0 569 062 describe an xe2x80x9cMEAxe2x80x9d (Membrane Electrode Assembly) for use in a PEM fuel cell, in which two catalytically active, cathode- and anode-side layers are applied as electrodes to a polymer electrolyte membrane.
These layers consist of finely disperse carbon powder in which catalyst particles are present. On the anode side, the particles should have a pore size of from 9 to 11 nm, while a pore size of 6 to 8 nm obtains on the cathode side.
The object of the present invention is to provide a method of discharging reaction water from fuel cells and a fuel cell for carrying out the method, which overcome the above-noted deficiencies and disadvantages of the prior art devices and methods of this general kind, and which implements the discharge of reaction water in PEM fuel cellsxe2x80x94comprising one porous layer each disposed on the cathode and on the anodexe2x80x94in such a way that neither humidification of the reaction gases nor elevated gas pressures are required.
With the above and other objects in view there is provided, in accordance with the invention, a method of discharging reaction water in a PEM fuel cell comprising an electrolyte membrane disposed between an anode and a cathode, the method which comprises placing one porous layer each on the cathode and on the anode and thereby forming a hydrophobic layer on the cathode having a smaller pore size than the porous layer on the anode, and discharging reaction water through the anode.
In other words, the objects of the invention are satisfied by the hydrophobic layer on the cathode side which has a smaller pore size than the anode-side layer and by the reaction water being discharged through the anode.
The invention therefore consists in discharging the reaction water on the anode side, with the advantage that gas humidification can be dispensed with and no elevated pressure is required, the invention providing a xe2x80x9cgas conduction layerxe2x80x9d on the cathode side. This gas conduction layer is gas-permeable, but impermeable to liquid water. Since during operation of the fuel cellxe2x80x94depending on the loadxe2x80x94water is being formed continuously as a liquid, the internal pressure in the cell on the cathode side increases and the water is forced through the electrolyte membrane to the anodexe2x80x94and through the anodexe2x80x94whence it is removed by means of an excess reactant gas stream, i.e. is transported from the fuel cell. Humidification of the reaction gas on the anode side need not be ruled out as a matter of principle however. This is the case, for example, if the reaction gas which carries off the water is recirculated.
The inventive approach offers the following advantages:
The cathode gas (oxidant), namely air or oxygen, need not be humidified, i.e. it can be supplied to the fuel cell in dry form without the electrolyte membrane becoming desiccated and damaged.
The anode gas, namely hydrogen, likewise need not be humidified, since all of the reaction water is transported to the anode and there ensures adequate humidity. Desiccation during operation cannot occur therefore.
The problems which arise in controlling the water budget in PEM fuel cells on the cathode side are overcome with the method according to the invention, in that the discharge of water takes place systematically on the anode side. This means that it is not possible for water droplets in the porous gas conduction layer on the cathode to give rise to inert gas blankets (N2) which inhibit the diffusion of the oxygen toward the catalyst layer.
The effective pressure increase is achieved by means of an internal barrier layer. This means that the system works independently of the reaction pressures. No differential pressure is required which has to be achieved externally, e.g. via an air compressor.
With the above and other objects in view there is also provided, in accordance with a further feature of the invention, a PEM fuel cell for performing the above-noted method. The PEM fuel cell comprises an anode, a cathode, an electrolyte membrane between the anode and the cathode, a first porous, electron-conducting layer disposed on the anode and a second porous, electron-conducting layer disposed on the cathode. The second layer on the cathode side is hydrophobic and has, at least on a surface thereof, a smaller pore size than the first layer on the anode side.
In other words, the apparatus for implementing the method according to the invention, i.e. a fuel cell, includesxe2x80x94in addition to an anode, a cathode, and an electrolyte membrane (between anode and cathode)xe2x80x94one porous, electron-conducting layer each disposed on the anode and on the cathode, the layer on the cathode side (gas conduction layer) being hydrophobic and having, at least on the surface, a smaller pore size than the layer on the anode side. Thus the gas conduction layer forms a barrier to liquid water.
The gas conduction layer preferably has a smaller pore size, in the surface adjoining the cathode, than the layer on the anode side. Such an embodiment can be implemented for example by means of a gas conduction layer having an asymmetric pore structure. This has the advantage that the delivery of the reaction gas to the cathode is impeded to a relatively minor extent, this being important, in particular, if the cell is operated with air.
The gas conduction layer can be present as a uniform layer having the specific pore size. Alternatively, however, it can consist of a sequence of layers such that a thin barrier layer, i.e. a layer having the specific pore size, is disposed between the electron-conducting layer present in fuel cells and the cathode. Such a design likewise has the advantagexe2x80x94in addition to being readily implementablexe2x80x94of only minor retardation of the delivery of the reaction gas.
In accordance with an added feature of the invention, therefore, the second layer on the cathode side has a smaller pore size, in the surface adjoining the cathode, than the first layer on the anode.
In accordance with an additional feature of the invention, the second layer, i.e., the gas conduction layer on the cathode is formed of an aerogel or a xerogel comprising carbon. Such layers, which are electron-conducting, can be produced in a relatively simple manner with the specific pore size required to prevent the passage of water.
Carbon aerogels or xerogels are known per se (cf. DE 195 23 382 A1); they are prepared e.g. by pyrolysis of aerogels based on organic compounds. The aerogels or xerogels used, in particular, are those based on resorcinol and formaldehyde (as monomers). Apart from resorcinol (1,3-dihydroxybenzene), other phenolic compounds can also be used however, e.g. phenol itself and the other dihydroxybenzenes, i.e. pyrocatechol and hydroquinone, and trihydroxy-benzenes such as pyrogallol and phloroglucinol, and also bisphenol A. The phenolic ring can also carry further substituents, e.g. alkyl groups, substituted alkyl groups, such as xe2x80x94CH2OH, and carboxyl groups, i.e. compounds such as alkyl phenols and dihydroxybenzoic acids can be used, for example. Instead of the phenolic components, compounds such as melamine can be used as an alternative. Furthermore, the formaldehyde can be replaced by other aldehydes, e.g. by furfural (xcex1-furfurylaldehyde).
In accordance with another feature of the invention, the second layer has a support matrix, i.e., the aerogel or xerogel layer advantageously includes a matrix, the mechanical stability of the relatively thin layer thus being enhanced. The matrix preferably consistsxe2x80x94at least in partxe2x80x94of organic material. Potentially suitable for this purpose are, in particular, cellulose, polyamides, polyesters and phenolic resins, especially Novolaks. The organic material can be in the form of porous membranes and flexible fiber webs and fibrous tissues. Alternatively, however, the matrix can consist of inorganic material, especially carbon fibers, aluminum oxide fibers, zirconium dioxide fibers or silicon dioxide fibers.
Alternatively, the gas conduction layer can consist of a carbon paper or carbon fabric whose cathode-side surface is hydrophobic, i.e. acts as a barrier to liquid, and which has a specific pore size. For this purpose, the surface can, for example, have a fine powder of carbon black, which is electron-conducting, and/or poly(tetrafluorethylene) (PTFE) incorporated thereinto.
In accordance with a concomitant feature of the invention, the first layer on the anode consists of porous carbon paper or carbon fabric employed customarily in PEM fuel cells. This layer, which can likewise be hydrophobic, generally hasxe2x80x94like the gas conduction layerxe2x80x94a layer thickness of from 100 to 300 xcexcm. As a matter of principle, these layers should be as thin as possible while still being capable of being handled mechanically.
Other features which are considered as characteristic for the invention are set forth in the appended claims.
Although the invention is described herein as embodied in a method of discharging reaction water in PEM fuel cells and a corresponding fuel cell, it is nevertheless not intended to be limited to the details given, since various modifications and structural changes may be made therein without departing from the spirit of the invention and within the scope and range of equivalents of the claims.
The construction and method of operation of the invention, however, together with additional objects and advantages thereof will be best understood from the following description of specific embodiments and examples.